The present invention relates to novel biarylalkylenecarbamic acid derivatives and agricultural and horticultural fungicides containing them as active ingredients.
The biarylalkylenecarbamic acid derivatives as the compounds of the present invention have not been known to have excellent fungicidal activity although a number of carbamic acid derivatives have been reported so far.
The present inventors have conducted extensive research to develop novel agricultural and horticultural fungicides and have found out that the biarylalkylenecarbamic acid derivatives of the present invention (hereinafter referred to as the compounds of the present invention) are novel compounds which have not been reported in the literature and show remarkable effects as agricultural and horticultural fungicides. The present invention is accomplished on the basis of the discovery.
Namely, the present invention provides biarylalkylenecarbamic acid derivatives represented by general formula (I): 
{wherein X is a halogen atom, a (C1-C6) alkyl group, a (C1-C6) alkoxy group, a (C1-C4) haloalkyl group or a (C1-C4) haloalkoxy group, n is 0 or an integer of from 1 to 4, R1 is a (C1-C6) alkyl group, a (C2-C6) alkenyl group, a (C2-C6) alkynyl group, a (C3-C6) cycloalkyl group or a (C1-C4) haloalkyl group, R2 is a hydrogen atom, a (C1-C6) alkyl group, a (C2-C6) alkenyl group, a (C2-C6) alkynyl group, a (C1-C4) alkoxy group, a (C1-C6) alkoxy (C1-C4) alkyl group, a (C1-C6) alkylthio (C1-C4) alkyl group, a (C1-C4) haloalkyl group, a (C1-C6) alkylcarbonyl group, a phenylcarbonyl group, a (C1-C4) alkoxycarbonyl group or an aryl (C1-C4) alkyl group [which may be substituted with a halogen atom, a (C1-C3) alkyl group or a (C1-C3) alkoxy group], A is a (C1-C7) alkylene group which may be branched, G is an oxygen atom, a sulfur atom or a groupxe2x80x94NRxe2x80x94 [wherein R3 is a hydrogen atom or a (C1-C4) alkyl group], and Q is a group represented by general formula: 
wherein Y is a halogen atom, nitro, cyano, hydroxy, a (C1-C6) alkyl group, a (C2-C6) alkenyl group, a (C2-C6) alkynyl group, a (C3-C6) cycloalkyl group, a (C3-C6) cycloalkyl (C1-C4) alkyl group, a (C1-C6) alkoxy group, a (C2-C6) alkenyloxy group, a (C2-C6) alkynyloxy group, a (C3-C6) cycloalkoxy group, a (C1-C6) alkylthio group, a (C1-C6) alkylsulfinyl group, a (C1-C6) alkylsulfonyl group, a (C1-C4) alkoxy (C1-C4) alkyl group, a (C1-C4) alkylthio (C1-C4) alkyl group, a (C1-C4) haloalkyl group, a (C1-C4) haloalkoxy group, a (C1-C4) haloalkylthio group, a (C1-C4) haloalkylsulfinyl group, a (C1-C4) haloalkylsulfonyl group, a (C1-C4) alkylcarbonyl group, a (C1-C4) alkoxycarbonyl group, a group xe2x80x94CONR4R5 [wherein R4 and R5 which may be the same or different, are hydrogen atoms or (C1-C4) alkyl groups], an amino group, a mono(C1-C4) alkylamino group, a di(C1-C4) alkylamino group, a (C1-C4) alkylcarbonylamino group, an aryl group [which may be substituted with a halogen atom, a (C01-C4) alkyl group or a (C1-C4) alkoxy group], an aryloxy group [which may be substituted with a halogen atom, a (C1-C4) alkyl group or a (C1-C4) alkoxy group], an aryl (C1-C4) alkoxy group [which may be substituted with a halogen atom, a (C1-C4) alkyl group or a (C1-C4) alkoxy group], or may form a methylenedioxy group together with an adjacent Y, and m is 0 or an integer of from 1 to 5} and agricultural and horticultural fungicides containing them as active ingredients.
The symbols and terms used herein are explained below.
A halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
An expression such as (C1-C6) means that the carbon number of the preceded group is, in this case, from 1 to 6.
A (C1-C6) alkyl group is a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3,3-dimethylbutyl or the like.
A (C3-C6) cycloalkyl group is, for example, cyclopropyl, cyclopentyl, cyclohexyl or the like.
A (C1-C4) haloalkyl group is a linear or branched alkyl group substituted with halogen atom(s) such as fluoromethyl, chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, pentafluoroethyl or the like.
A (C2-C6) alkenyl group is a linear or branched alkenyl group such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl or the like.
A (C2-C6) alkynyl group is a linear or branched alkynyl group such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl or the like.
A (C1-C6) alkoxy group is an alkyloxy group having such an alkyl moiety as mentioned above.
A (C2-C6) alkenyloxy group is an alkenyloxy group having such an alkenyl moiety as mentioned above.
A (C2-C6) alkynyloxy group is an alkynyloxy group having such an alkynyl moiety as mentioned above.
A (C3-C6) cycloalkoxy group is a cycloalkyloxy group having such a cycloalkyl moiety as mentioned above.
A (C1-C4) haloalkoxy group is a haloalkyloxy group having such a haloalkyl moiety as mentioned above.
A (C1-C6) alkylthio group is an alkylthio group having such an alkyl moiety as mentioned above.
A (C1-C6) alkylsulfinyl group is an alkylsulfinyl group having such an alkyl moiety as mentioned above.
A (C1-C6) alkylsulfonyl group is an alkylsulfonyl group having such an alkyl moiety as mentioned above.
A (C1-C4) haloalkylthio group is a haloalkylthio group having such a haloalkyl moiety as mentioned above.
A (C1-C4) haloalkylsulfinyl group is a haloalkylsulfinyl group having such a haloalkyl moiety as mentioned above.
A (C1-C4) haloalkylsulfonyl group is a haloalkylsulfonyl group having such a haloalkyl moiety as mentioned above.
A (C1-C7) alkylene group which may be branched is, for example, xe2x80x94CH2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94 or the like.
An aryl group is phenyl, xcex1-naphthyl, xcex2-naphthyl or the like.
An aryl (C1-C4) alkyl group is benzyl or the like.
An aryloxy group is phenoxy, naphthoxy or the like.
An aryl (C1-C4) alkoxy group is benzyloxy or the like.
Specific examples of the compounds of the present invention are given below in Tables 1 to 53. However, the compounds of the present invention are by no means restricted to those specific examples. The compound Nos. are referred to in the description hereinafter.
Typical processes for production of the biarylalkylenecarbamic acid derivatives as the compounds of the present invention are exemplified below. 
(wherein A, G, Q, R1, R2, X and n are the same as defined above, and Z is a halogen atom.)
A compound (I) of the present invention is obtainable by reaction of a compound (II) with a compound (III) in an inert solvent in the presence of a base.
With respect to the amounts of the starting compounds used in the reaction, the compound (III) relative to the compound (II) is appropriately selected within the range of from 0.5 to 3.0 eq, preferably from 0.8 to 1.5 eq.
As the inert solvent to be used in the reaction, any solvent that does not inhibit the progress of the reaction, and for example, ketones such as acetone, methyl ethyl ketone or cyclohexanone, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme and diglyme, esters such as ethyl acetate and methyl acetate, halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride and tetrachloroethane, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene, nitrites such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolinone and dimethyl sulfoxide may be used. These inert solvents may be used alone or in combination.
In the reaction, the base may be inorganic or organic, and as inorganic bases, carbonates or hydroxides of alkali metal atoms or alkaline earth metal atoms, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide or hydrides of alkali metal atoms such as lithium hydride and sodium hydride may be used, and as organic bases, for example, triethylamine, diisopropylethylamine and pyridine may be used. These bases may be used alone or in combination. The amount of a base is appropriately selected within the range of from 0.5 to 3.0 eq, preferably from 0.8 to 2.0 eq, based on the compound (II).
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, preferably from xe2x88x9240xc2x0 C. to 40xc2x0 C. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization. 
(wherein A, Q, R1, R2, X and n are the same as defined above.)
A compound (I-1) of the present invention is obtainable by reaction of a compound (II) with a compound (IV) in an inert solvent.
With respect to the amounts of the starting compounds used in the reaction, the compound (IV) relative to the compound (II) is appropriately selected within the range of from 0.5 to 3.0 eq, preferably from 0.8 to 2.0 eq.
In the reaction, as the inert solvent, the solvents exemplified for Process 1 may be used.
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, preferably from xe2x88x9210xc2x0 C. to the boiling point of the inert solvent. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization. 
(wherein A, G, Q, R1, R2, X and n are the same as defined above, and Z2 is a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group or a mesyloxy group.)
A compound (I) of the present invention is obtainable by reaction of a compound (V) with a compound (VI) in an inert solvent in the presence of a base.
With respect to the amounts of the starting compounds used in the reaction, the compound (VI) relative to the compound (V) is appropriately selected within the range of from 0.5 eq to an excess, preferably from 0.8 to 2.0 eq.
In the reaction, as the inert solvent, solvents exemplified for Process 1 may be used.
In the reaction, as the base, the bases exemplified for Process 1 may be used. The amount of a base is appropriately selected within the range of from 1 eq to an excess, preferably from 1 eq to 2 eq, based on the compound (V).
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the reaction mixture to be used, preferably from xe2x88x9210xc2x0 C. to the boiling point of the reaction mixture. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization. 
(wherein A, G, Q, R1, X and n are the same as defined above.)
A compound (I-2) of the present invention is obtainable by reaction of a compound (VII) with a compound (VIII) in an inert solvent.
With respect to the amounts of the starting compounds used in the reaction, the compound (VIII) relative to the compound (VII) is appropriately selected within the range of from 1 eq to an excess, preferably from 1.0 to 2.0 eq.
In the reaction, as the inert solvent, the solvents exemplified for Process 1 may be used.
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the reaction mixture to be used, preferably from xe2x88x9210xc2x0 C. to the boiling point of the reaction mixture. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization. 
(wherein A, G, Q, R1, X and n are the same as defined above, R2 is R2 (which is the same as defined above) exclusive of a hydrogen atom, and Z2 is a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group or a mesyloxy group.)
A compound (I-3) of the present invention is obtainable by reaction of a compound (I-2) of the present invention with a compound (IX) in an inert solvent in the presence of a base.
With respect to the amounts of the starting compounds used in the reaction, the compound (IX) relative to the compound (I-2) is appropriately selected within the range of from 1 eq to an excess, preferably from 1.0 to 3.0 eq.
In the reaction, as the inert solvent, the solvents exemplified for Process 1 may be used.
In the reaction, as the base, the bases exemplified for Process 1 may be used. The amount of a base is appropriately selected within the range of from 1 eq to an excess, preferably from 1 eq to 2 eq, based on the compound (I-2).
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization. 
(wherein A, G, Q, R1, R2, X and n are the same as defined above, and Z3 is a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group.)
A compound (I) of the present invention is obtainable by reaction of a compound (X) with a compound (XI) in an inert solvent in the presence of a zero-valent palladium catalyst (XII) and a base by a conventional method (for example, Synthetic Communications, vol. 11, p.513 (1981)).
With respect to the amounts of the starting compounds used in the reaction, the compound (XI) relative to the compound (X) is appropriately selected within the range of from 1 eq to an excess, preferably from 1.0 eq to 2.0 eq.
As the inert solvent to be used in the reaction, any solvent that does not inhibit the progress of the reaction, and for example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme and diglyme, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene, nitrites such as acetonitrile, alcohols such as methanol, ethanol, propanol and 2-propanol, esters such as methyl acetate and ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide and water may be used. These solvents may be used alone or in combination.
As the zero-valent palladium catalyst to be used in the reaction, a palladium complex such as tetrakis(triphenylphosphine)palladium (0), bis(dibenzylideneacetone)palladium (0) or tris(dibenzylideneacetone)dipalladium (0) may be used. The amount of a zero-valent palladium catalyst is appropriately selected within the range of from 0.001 eq to 1 eq, preferably from 0.01 eq to 0.2 eq, based on the compound (X).
As the base to be used in the reaction, carbonates or hydroxides of alkali metal atoms or alkaline earth metal atoms, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide may be used. These bases may be used alone or in combination. The amount of a base is appropriately selected within the range of from 1.0 eq to an excess, preferably from 1 eq to 2 eq, based on the compound (X).
The reaction temperature is selected within the range of from xe2x88x9270xc2x0 C. to the boiling point of the inert solvent to be used, preferably from room temperature to the boiling temperature of the reaction mixture. The reaction time is usually selected within the range of from several minutes to 48 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization.
The boric acid derivative as the compound (XI) is obtainable by a known method (for example, Jikken Kagaku Koza, 4th edition, vol. 24, p.80, Maruzen). 
(wherein A, G, Q, R1, X, n and Z2 are the same as defined above, and M is a sodium atom or a potassium atom.)
A compound (I-2) of the present invention is obtainable by reaction of a compound (V) with a compound (XIII) and a compound (VIII) in an inert solvent.
With respect to the amounts of the starting compounds used in the reaction, the compound (XIII) relative to the compound (V) is appropriately selected within the range of from 1.0 to 5.0 eq, preferably from 1.0 to 3.0 eq, and the compound (VIII) relative to the compound (V) is appropriately selected within the range of from 1.0 eq to an excess.
In the reaction, as the inert solvent, the solvents exemplified for Process 1 may be used.
The reaction temperature is selected within the range of from room temperature to the boiling point of the reaction mixture to be used, preferably from 30xc2x0 C. to the boiling point of the reaction mixture. The reaction time is usually selected within the range of from 1 hour to 24 hours, though it depends on the reaction temperature, the amounts of the reactants and the like. After the reaction, the desired product is isolated from the reaction system by a conventional method and, if necessary, purified by column chromatography or recrystallization.
Preparation of Compounds (II)
Compounds (II) can be synthesized in accordance with Processes a to d as follows. However, its synthesis is not restricted to these processes. 
(wherein A, Q, R1, X, n and Z3 are the same as defined above.)
A compound (II) is obtainable by reaction of a compound (XIV) with a compound (XI) in an inert solvent in the presence of a compound (XII) and a base in accordance with Process 6 as mentioned above. 
(wherein Q, R1, X, n and Z3 are the same as defined above, and Axe2x80x2 is a (C1-C6) alkylene group which may be branched or a bond.)
A compound (II-1) is obtainable by reduction of a compound (XV) and subsequent reaction of the resulting compound (XVI) with a compound (XI) in the presence of a compound (XII) and a base in an inert solvent in accordance with Process 6 as mentioned above.
A compound (II-1) is also obtainable by reaction of a compound (XV) with a compound (XI) in the presence of a compound (XII) and a base in an inert solvent in accordance with Process 6 as mentioned above and subsequent reduction of the resulting compound (XVII). 
(wherein Axe2x80x2, Q, X, n and Z3 are the same as defined above.)
A compound (II-2) is obtainable by reduction of a compound (XVIII) followed by reaction of the resulting compound (XIX) with a compound (XI) in the presence of a compound (XII) and a base in an inert solvent in accordance with Process 6 as mentioned above.
A compound (II-2) is also obtainable by reaction of a compound (XVIII) with a compound (XI) in the presence of a compound (XII) and a base in an inert solvent in accordance with Process 6 as mentioned above, followed by reduction of the resulting compound (XX). 
(wherein Q, X, n and Z3 are the same as defined above, and R6 is an alkyl group.)
A compound (II-3) is obtainable by conversion of a compound (XXI) into a compound (XXIII) by reductive amination or by reaction with a hydroxylamine hydrochloride in an inert solvent followed by reduction of the resulting compound (XXII), and subsequent reaction of the resulting compound (XXIII) with a compound (XI) in the presence of a compound (XII) and a base in an inert solvent in accordance with Process 6 as mentioned above. 
(wherein A, Q, X, n and Z2 are the same as defined above.)
A compound (V) is obtainable by halogenation of a compound (XXV), or halogenation, mesylation or tosylation of a compound (XXVI). 
(wherein A, Q, X and n are the same as defined above.)
A compound (VII) is obtainable by known methods (for example, Shin Jikken Kagaku Koza, vol.14, p.1490, Maruzen).
Preparation of Compounds (X)
A compound (X) is obtainable in accordance with Processes 1-5 or Process 7 as a compound of general formula (I) wherein Q is Z3.